JP2011102794A - Irreversible temperature indicator and irreversible temperature indicator set using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an irreversible temperature indicator using a layer made of melting composition such as wax, where the color tone change after use is made clear and the convenience is improved by applying a porous layer having a high lower-layer masking property during non-use and high permeation transmission properties during wax dissolving, and to provide an irreversible temperature indicator set having a writing instrument allowing writing on the porous layer and allowing holding of a written character for a long time. <P>SOLUTION: In this irreversible temperature indicator, the porous layer 4 that is opaque in a liquid non-absorption state where a low refractive index pigment is fixed to a binder resin in a dispersed state and is made transparent in a liquid absorption state is disposed on a colored support 2, and a wax layer 5 dissolving at a specific temperature is disposed on the porous layer 4. Further, a transparent sheet 6 is disposed on the uppermost surface. The indicator set includes the irreversible temperature indicator 1, and the writing instrument including liquified composition in which solid material with a refractive index of 1.3-1.8 is dissolved in a liquified medium. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to an irreversible temperature indicator and an irreversible temperature indicator set using the irreversible temperature indicator. Furthermore, the present invention relates to an irreversible temperature indicator that expresses a clear color tone change above a specific temperature and an irreversible temperature indicator set using the irreversible temperature indicator.

Conventionally, a plurality of irreversible temperature indicators whose color tone changes when the temperature exceeds a specific temperature are disclosed (for example, see Patent Documents 1 to 3).
The irreversible temperature indicators of Patent Documents 1 and 2 are both laminated on colored paper using a meltable composition such as a solid wax that dissolves at a specific temperature, and the composition dissolves into colored paper. It is an indicator of the structure by which the color tone of colored paper is visually recognized by osmosis | permeation.
The irreversible temperature indicator is formed by directly laminating a layer made of a meltable composition (wax layer) on colored paper, so that the concealability is low, and the color tone of the lower layer of the wax layer can be visually recognized in an unused state. The color change was difficult to understand.

  On the other hand, the irreversible temperature indicator of Patent Document 3 is one in which Japanese paper is laminated between the wax layers laminated on the colored paper or the upper layer. Compared with the two-layer irreversible temperature indicator, Although the hiding property of the lower layer at the time of use is improved, the change in color tone after use cannot be clearly obtained due to the low permeability of the Japanese paper when the wax is dissolved.

Japanese Utility Model Publication 4-289 JP 59-164929 A JP 2001-83020 A

The present invention applies a porous layer that is highly irreversible temperature indicator using a layer made of a meltable composition such as wax, and has high concealment of the lower layer when not in use and high permeation permeability when dissolving the wax. Thus, the present invention provides a highly convenient irreversible temperature indicator in which the color change after use becomes clear.
Furthermore, the present invention provides an irreversible temperature indicator set provided with a writing tool that can be written on the porous layer of the irreversible temperature indicator and can retain written characters for a long period of time.

The present invention provides a porous layer that is opaque in a non-liquid-absorbing state in which a low refractive index pigment is fixed in a dispersed state on a binder resin and is transparent in the liquid-absorbing state on a colored support. A requirement is an irreversible temperature indicator comprising a wax layer that melts at a specific temperature on the layer.
Further, a wax layer that dissolves at a specific temperature is provided on a colored support, and a low refractive index pigment is fixed in a dispersed state on a binder resin on the wax layer. An irreversible temperature indicator comprising a porous layer that becomes transparent is required.
Further, a porous layer which is opaque in a non-liquid-absorbing state and transparent in a liquid-absorbing state in which a low refractive index pigment is fixed in a dispersed state on a binder resin on a colored support impregnated with a wax which dissolves at a specific temperature. An irreversible temperature indicator is required.
Furthermore, it is required that a transparent sheet is provided on the uppermost surface, and that the difference between the brightness value before dissolving the wax and the brightness value after dissolving the wax is 2.0 or more.
Furthermore, an irreversible temperature indicator set comprising the irreversible temperature indicator and a writing instrument containing a liquid composition in which a solid material having a refractive index of 1.3 to 1.8 is dissolved and / or dispersed in a liquid medium is a requirement. .
Further, the particle size of the solid material dispersed in the liquid medium is 10 μm or less, the liquid medium contains a shear thinning agent, and the writing instrument holds the ball rotatably. It is a requirement to be in the form of a ballpoint pen with a ballpoint tip held.

According to the present invention, the brightness difference between the color tone when not in use and the color tone after permeation and transmission due to wax dissolution at the time of use becomes extremely large, so an irreversible temperature indicator with a high indicator function that expresses a clear color tone change due to use. Can be provided. Therefore, the usage is wide and convenient.
Moreover, it is possible to write desired characters and marks on the porous layer of the indicator by handwriting, and the handwriting can be retained for a long period of time, so that it becomes a highly practical irreversible temperature indicator set.

It is a principal part longitudinal cross-sectional view of the Example of the irreversible temperature indicator of this invention. It is a principal part longitudinal cross-sectional view of the other Example of the irreversible temperature indicator of this invention. It is a principal part longitudinal cross-sectional view of the other Example of the irreversible temperature indicator of this invention. It is a principal part longitudinal cross-sectional view of the other Example of the irreversible temperature indicator of this invention. It is a principal part longitudinal cross-sectional view of the other Example of the irreversible temperature indicator of this invention. It is a principal part longitudinal cross-sectional view of the other Example of the irreversible temperature indicator of this invention. It is longitudinal section explanatory drawing of one Example of the writing instrument applied to the irreversible temperature indicator set of this invention.

Examples of the support include paper (general-purpose paper including synthetic paper and surface-treated paper), a resin film, a substrate surface of a base material such as a fabric, and a colored substrate as a whole. Is used. At that time, it is preferable that the color tone of the colored layer (colored portion) is dark.
In the case of the constitution of claim 3, that is, when the support is impregnated with wax, it is preferable to use colored paper (quality paper, etc.) or fabric with high permeability.

The wax is a meltable composition that is solid at room temperature and is laminated on a support or a porous layer, and is impregnated in a permeable support.
As the wax, a general-purpose one is applied, and esters are preferred. Specific examples include decyl myristate, cetyl caprate, stearyl caprate, stearyl laurate, palmitic acid, tripalmitin, stearic acid, acetoacetanilide, benzotriazole, pimelic acid, acetanilide, sebacic acid, adipic acid and the like. .
Moreover, when comprising the said wax layer, a general-purpose printing binder can be added, it can be made into an ink form, and can also be laminated | stacked by printing.

The porous layer is a layer in which a low refractive index pigment is fixed in a dispersed state together with a binder resin, and is made transparent by adhesion of a liquid.
Examples of the low refractive index pigment include silicic acid and salts thereof, barite powder, barium sulfate, barium carbonate, calcium carbonate, gypsum, clay, talc, alumina white, magnesium carbonate, and the like. It is in the range of 1.8, and when the liquid composition is absorbed, good transparency is exhibited.
Examples of the silicic acid salt include aluminum silicate, aluminum potassium silicate, sodium aluminum silicate, aluminum calcium silicate, potassium silicate, calcium silicate, calcium sodium silicate, sodium silicate, magnesium silicate, and magnesium potassium silicate.
The particle size of the low refractive index pigment is not particularly limited, but 0.03 to 10.0 μm is preferably used.
Two or more of the low refractive index pigments can be used in combination.
In addition, silicic acid is mentioned as a low refractive index pigment used suitably.
The silicic acid may be silicic acid produced by a dry process, but silicic acid produced by a wet process (hereinafter referred to as wet process silicic acid) is particularly effective and satisfies practicality.
This point will be described below.
Silicic acid is produced as amorphous amorphous silicic acid, and according to its production method, a dry process using a gas phase reaction such as thermal decomposition of silicon halide such as silicon tetrachloride (hereinafter referred to as dry process silicic acid) In general, the wet process silicic acid is the most suitable for the purpose of functioning as the porous layer intended by the present invention, although the wet process uses a liquid phase reaction such as decomposition by acid such as sodium silicate. .
This is because the dry process silicic acid and the wet process silicic acid have different structures, and the dry process silicic acid forms a three-dimensional structure in which the silicic acid is closely bound, whereas the wet process silicic acid is a long molecule formed by condensation of silicic acid It has a so-called two-dimensional structure part that forms an array.
Therefore, since the molecular structure becomes rough compared to the dry method silicic acid, when wet method silicic acid is applied to the porous layer, it is excellent in the diffused reflection of light in the dry state compared to the system using the dry method silicic acid, Therefore, it is guessed that the concealment property in a normal state becomes large.
In addition, in order to adjust the concealability in the normal state of the porous layer and the transparency in the liquid absorption state, other general-purpose low-refractive-index pigments can be used in combination with the wet method silicic acid.

The wet process silicic acid in the porous layer depends on properties such as particle size, specific surface area, oil absorption, etc., but in order to satisfy both the concealing property in the normal state and the transparency in the liquid absorbing state, it is applied. preferably the amount is ^{1g / m 2 ~30g / m 2} , more ^{preferably 5g / m 2 ~20g / m 2} . If it is less than 1 g / m ² , it is difficult to obtain sufficient concealability in a normal state, and if it exceeds 30 g / m ² , it is difficult to obtain sufficient transparency during liquid absorption.
The particle size of the silicic acid is not particularly limited, but 0.03 to 10.0 μm is preferably used.

The low refractive index pigment such as silicic acid is dispersed in a vehicle containing a binder resin as a binder, and is applied to a substrate, and then the volatile matter is dried to form a porous layer.
Examples of the binder resin include urethane resin, nylon resin, vinyl acetate resin, acrylic ester resin, acrylic ester copolymer resin, acrylic polyol resin, vinyl chloride-vinyl acetate copolymer resin, maleic resin, polyester resin, styrene. Resin, styrene copolymer resin, polyethylene resin, polycarbonate resin, epoxy resin, styrene-butadiene copolymer resin, acrylonitrile-butadiene copolymer resin, methyl methacrylate-butadiene copolymer resin, butadiene resin, chloroprene resin, melamine resin, and the above Each resin emulsion, casein, starch, cellulose derivative, polyvinyl alcohol, urea resin, phenol resin and the like can be mentioned.
The mixing ratio of the silicic acid and these binder resins depends on the type and properties of silicic acid, but is preferably 0.5 to 2 parts by weight of binder resin solids, more preferably 1 part by weight of silicic acid. 0.8 to 1.5 parts by weight. When the binder resin solid content is less than 0.5 parts by weight with respect to 1 part by weight of silicic acid, it is difficult to obtain a practical film strength of the porous layer, and when it exceeds 2 parts by weight, The permeability into the porous layer is deteriorated.
Since the porous layer has a small mixing ratio of the binder resin to the colorant as compared with a conventionally known general coating film, it is difficult to obtain a sufficient film strength. Therefore, in order to increase the scratch resistance, it is effective to use a nylon resin or a urethane resin among the binder resins. In this case, nylon resin and urethane resin can be used alone, but other binder resins can be used in combination depending on the type of support and the performance required for the coating. When a binder resin other than the urethane resin is used in combination, in order to obtain a practical film strength, it is preferable to contain 30% or more of the urethane resin in a solid content weight ratio in the binder resin of the porous layer.
In the binder resin, a crosslinkable resin can be further improved in film strength by adding an arbitrary crosslinking agent and crosslinking. Furthermore, it is possible to control the permeation time and the permeation degree by appropriately adding a dispersant or a surfactant.

In the porous layer, conventionally known titanium dioxide-coated mica, iron oxide-titanium dioxide-coated mica, iron oxide-coated mica, guanine, sericite, basic lead carbonate, acidic lead arsenate, bismuth oxychloride, etc. The color change can be diversified by adding metallic luster pigments and mixing of general dyes and pigments, fluorescent dyes and fluorescent pigments.
Moreover, a general-purpose reversible thermochromic pigment that changes color reversibly with temperature changes can be mixed to change the color depending on the environmental temperature.

The porous layer may be formed in a solid print form, or may be formed in an image form such as letters, symbols, alphanumeric characters, designs, and the like.
The porous layer is a conventionally known means such as screen printing, offset printing, gravure printing, coater, tampo printing, transfer printing means, brush coating, spray coating, electrostatic coating, electrodeposition coating, flow coating, It can be formed by roller coating, dip coating, or the like.

  Furthermore, by disposing a non-discoloring layer (colored layer) on or near the porous layer, it is possible to improve design and diversify display information.

A transparent sheet can be laminated on the uppermost surface of the indicator provided with the porous layer and wax. With the sheet, the resistance of the indicator can be improved, and leakage during wax melting can be suppressed.
The material of the transparent sheet is not particularly limited, and plastic sheets such as polyethylene, polypropylene, polyvinyl chloride, polyethylene terephthalate, polymethyl methacrylate, polyacrylate, polystyrene, polycarbonate, cellulose triacetate, cellulose diacetate, polyvinyl alcohol, and polyamide. A glass plate can be exemplified, but plastic sheets such as polyethylene, polypropylene, polyethylene terephthalate, and polyvinyl chloride, which are rich in flexibility and excellent in safety, are preferably used.
The transparent sheet may be translucent or colored and can be provided on the back side of the colored support.

When the irreversible temperature indicator is used as a set with a writing instrument capable of writing on the porous layer, the transparent sheet is preferably provided as a separate body. Thereby, since the transparent sheet can be laminated after the user writes on the porous surface, resistance can be imparted to the formed handwriting, and a more stable display surface can be maintained for a long time.
As the transparent sheet that can be stuck, one in which an adhesive is applied to the edge or the entire surface of the sheet can be applied, and a transparent adhesive is suitable as the adhesive.

  An adhesive layer can also be provided on the back surface of the support. The adhesive layer can be used by sticking to a place where a temperature change is desired to be used, and therefore, the usage is widened.

The irreversible temperature indicator obtained by the above-described configuration includes a lightness value (Vd) measured in an unused state (non-liquid absorption state of the porous layer) and a lightness value measured after use (liquid absorption state of the porous layer) ( Vw) is set so that the brightness difference (that is, Vd−Vw) is 2.0 or more.
The above value indicates that the greater the lightness value (Vd) measured in the non-absorbing state of the porous layer, the higher the concealing property and the lower the color tone is less visible, and the lightness value measured when the porous layer is in the liquid-absorbing state. The smaller (Vw), the higher the transparency and the lower the color tone can be clearly seen. In particular, when the lightness difference (Vd−Vw) between (Vd) and (Vw) is 2.0 or more, the color change before and after use can be more clearly confirmed. Even when the indicator is a small size, high functionality can be expressed.

The irreversible temperature indicator can be used together with a writing instrument containing a liquid composition in which a solid material having a refractive index of 1.3 to 1.8 is dissolved and / or dispersed in a liquid medium.
The writing instrument is used for writing on the porous layer of the irreversible temperature indicator, and the desired handwriting formed can be held semipermanently without evaporating and disappearing.

The liquid composition accommodated in the writing instrument is to permeate the porous layer and make it transparent or translucent to make the image visible. Even if the medium that has permeated the porous layer evaporates, the liquid composition is contained in the liquid composition. Since the contained solid matter remains, the image is permanently visible.
The medium used for the liquid composition is preferably water from the viewpoint of safety and cost, but is not limited thereto, and may be an organic solvent or a mixture of an organic solvent and water.
The organic solvent is appropriately selected from hydrocarbons, monohydric alcohols, polyhydric alcohols and derivatives thereof, ethers and acetals, ketones, esters, fatty acids and phenols, nitrogen compounds, and the like. In particular, aliphatic esters such as liquid paraffin, vegetable oil, and adipic acid ester, and glycols such as propylene glycol and glycerin are preferably used because they are superior in safety compared to other organic solvents.

The solid substance dissolved and / or dispersed in the medium is a substance that exhibits a solid state at 20 ° C., and remains in the porous layer even when the medium dries, so that the image can be viewed permanently. Of 1.3 to 1.8, preferably 1.4 to 1.7.
This is because the refractive index of the low refractive index pigment contained in the porous layer of the indicator is in the range of 1.4 to 1.8, so that the solid matter that has penetrated into the layer has the same refractive index as the low refractive index pigment. This is because the layer can be provided with good transparency and the effect of visually recognizing the color tone of the lower layer can be exhibited permanently.
Therefore, by using the solid material, an image formed on the porous layer can be preserved with the same shape and color tone as the initial one even after aging.

  The solid material is not particularly limited as long as it is an organic or inorganic material that exhibits a solid state at 20 ° C. and has a refractive index in the range of 1.3 to 1.8. Examples thereof include ionomer resins, amino acids, and the like. Polyacrylamide resin, isobutylene resin, isobutylene-maleic anhydride copolymer resin, acrylonitrile-acrylate-styrene copolymer resin, acrylonitrile-ethylene-styrene copolymer resin, acrylonitrile-styrene copolymer resin, acrylonitrile-butadiene-styrene copolymer resin, Acrylonitrile-vinylidene chloride copolymer resin, acrylonitrile-chlorinated polyethylene-styrene copolymer resin, butadiene-styrene-methyl methacrylate terpolymer, vinyl chloride resin, ethylene-propylene copolymer resin, ethylene acrylic acid Steal copolymer, ethylene-methacrylic acid copolymer resin, ethylene-vinyl chloride copolymer resin, vinyl chloride-propylene copolymer resin, vinyl chloride-vinylidene copolymer resin, ethylene-vinyl acetate copolymer resin, chlorinated ethylene-vinyl acetate Copolymer resin, ethylene-vinyl acetate-vinyl chloride copolymer resin, ethylene-vinyl alcohol copolymer resin, polyvinyl chloride resin, chlorinated polyethylene resin, chlorinated polypropylene resin, carboxyvinyl polymer, ketone resin, norbornene resin, polyamide resin Copolyamide resin, polyamideimide resin, methoxymethylated polyamide, polycarbonate resin, polybutadiene resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polystyrene resin, high impact polystyrene Fat, styrene-maleic acid copolymer resin, acrylic-styrene copolymer resin, polyacetal resin, polyvinyl formal resin, polyvinyl butyral resin, polyarylate resin, polyetherimide resin, polyether resin, polyethylene resin, polypropylene resin, polymethylstyrene Resin, acrylic ester resin, vinyl acetate-acrylic ester copolymer resin, styrene-acrylic ester copolymer resin, polyvinyl acetate resin, polymethyl methacrylate resin, epoxy acrylate resin, alkylphenol resin, rosin modified phenol resin, rosin modified Alkyd resin, Funol resin modified alkyd resin, Styrene modified alkyd resin, Epoxy modified alkyd resin, Acrylic modified alkyd resin, Amino alkyd resin, Butyral resin, Poly Urethane resin, vinyl chloride-vinyl acetate copolymer resin, epoxy resin, alkyd resin, styrene-butadiene copolymer resin, unsaturated polyester resin, saturated polyester resin, vinyl chloride-acrylic copolymer resin, polyvinyl acetate resin, polyvinylidene chloride Copolymer resin, polyolefin copolymer resin, rosin ester resin, polyisobutylene resin, isoprene rubber, butyl rubber, cyclized rubber, chlorinated rubber, polyvinyl alkyl ether resin, fluorine resin, silicone resin, phenol resin, petroleum hydrocarbon Resin, toluene resin, xylene resin, methacrylate ester copolymer resin, melamine resin, urea resin, phenoxy resin, benzoguanamine resin, polyethylene oxide, polyethylene glycol, polyvinyl pyrrolidone, vinyl pyrrolidone-vinegar Vinyl copolymer resin, vinyl pyrrolidone-vinyl imidazole copolymer resin, vinyl pyrrolidone-vinyl imidazole methyl sulfate copolymer resin, vinyl pyrrolidone-sodium methacrylate copolymer resin, vinyl pyrrolidone-vinyl caprolactam copolymer resin, polyvinyl polypyrrolidone, Polyvinyl caprolactam, polyvinyl pyrrolidone-vinyl imidazole, polyvinyl alcohol, modified polyvinyl alcohol, polyacrylate, polymethacrylate, polyvinyl pyridine, polyacrylamide, polyethyleneimine, polyvinyl methyl ether, styrene-maleic anhydride copolymer resin, methyl vinyl ether -Maleic anhydride copolymer resin, synthetic resin such as polyphosphate, or oligomer.

  Cellulose acetate, cellophane, cellulose acetate propionate, cellulose acetate butyrate, nitrocellulose, methylcellulose, ethylcellulose, carboxymethylcellulose, carboxymethylethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose and other cellulose derivatives, starch, dialdehyde starch, carboxymethylated Starch, hydroxyethylated starch, starch derivatives such as phosphate starch, dextrin, gelatin, glue, rosin, shellac, casein, sodium caseinate, carnauba wax, glue, alginic acid, sodium alginate, propylene glycol alginate, collagen, elastin, Arabic gum, ester gum, guar gum, glycyrrhizin, copalgo , Tarakantogamu, Danmarugomu, gallnut, gallic, tannic acid, hyaluronic acid, camphor, synthetic camphor, lactose, glucose, pectin, polyphenols, beeswax, Japan wax, gallic acid, natural products such as pyrogallol, or semi-synthetic resin.

Solid fats such as coconut oil, palm oil, beef tallow, hydrogenated oil, higher fatty acid, higher alcohol, fatty acid ester, oxyacid ester, polyhydric alcohol fatty acid ester, alkyl glyceryl ether fatty acid ester.
Fatty acid soap, N-acyl amino acid salt, polyoxyethylene carboxylate, polyoxyethylene alkyl ether carboxylate, acylated peptide, alkylsulfonate, alkylbenzenesulfonate, alkylnaphthalenesulfonate, naphthalenesulfonate Formalin condensate, melamine sulfonate-formalin condensate, dialkyl sulfosuccinate ester salt, alkyl sulfosulfosuccinate, polyoxyethylene alkyl sulfosuccinate, alkyl sulfoacetate, α-olefin sulfonate, N-acyl-N -Methyl taurine salt, dimethyl-5-sulfoisophthalate sodium salt, sulfated oil, alkyl sulfate, secondary higher alcohol sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene fat Alkanolamide sulfate, polyoxyethylene alkyl phenyl ether sulfate, monoglyculate, fatty acid alkyl amide sulfate sulfate, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkyl phenyl ether phosphate, alkyl phosphate, aliphatic Amine salt, aliphatic quaternary ammonium salt, benzalkonium chloride salt, benzethonium chloride, pyridinium salt, imidazolinium salt, alkyl dimethyl bentine, aminocarboxylate, imidazolium bentine, lecithin, lecithin derivative, alkylamine oxide, poly Oxyethylene alkyl ether, polyoxyethylene secondary alcohol ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene Lenlanolin derivative, alkylphenol formalin condensate ethylene oxide derivative, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene castor oil, polyoxyethylene sorbitan fatty acid ester, polyoxy Ethylene sorbitol fatty acid ester, polyoxyethylene glycol fatty acid ester, ethylene glycol fatty acid ester, glycerin fatty acid ester, polyglycerin fatty acid ester, sorbitan fatty acid ester, propylene glycol fatty acid ester, fatty acid alkanolamide, polyoxyethylene fatty acid amide, polyoxyethylene alkylamine , Fluoroalkyl carboxylates Disodium N-perfluorooctanesulfonyl glutamate, sodium 3- [fluoroalkyloxy] -1-alkylsulfonate, sodium 3- [ω-fluoroalkanoyl-N-ethylamino] -1-propanesulfonate, N- [3 -(Perfluorooctanesulfonamido) propyl] -N, N dimethyl-N-carboxymethyleneammonium bentyne, N- [3- (perfluorooctanesulfonamido) propyl] -N, N-dimethyl-N-carboxymethyleneammonium bentine Perfluoroalkylcarboxylic acid, perfluorooctanesulfonic acid diethanolamide, perfluoroalkylsulfonate, N-propyl-N- (2-hydroxyethyl) perfluorooctanesulfonamide, perfluoroa Rualkyl-N-ethylsulfonylglycine salt, bis (N-perfluorooctylsulfonyl-N-ethylaminoethyl) phosphate, monoperfluoroalkylethyl phosphate ester, polyoxyethylene allyl glycidyl nonyl phenyl ether sulfate salt, polyoxy Surfactants such as ethylene allyl glycidyl nonyl phenyl ether, polyoxyethylene nonyl propenyl phenyl ether, polyoxyethylene nonyl propenyl phenyl ether sulfate ammonium salt.

Polysaccharides such as starch sugar, dextran, curdlan, pullulan, cycloamylose, chitin, chitosan, hyaluronic acid, chondroitin sodium sulfate.
G-glycosides such as D-sorbitol, mannitol, maltitol, inositol, phytic acid, and arbutin.

  Vitamin A, vitamin B1, vitamin B2, vitamin B6, vitamin B12, vitamin C, calcium ascorbate, vitamin D, vitamin E, vitamin F, vitamin G, vitamin H, vitamin K, vitamin L, vitamin M, vitamin P, vitamin Vitamins such as R, vitamin S, vitamin T, vitamin U, vitamin V, vitamin W, vitamin X, vitamin Y, pantothenic acid, nicotinic acid, lipoic acid and lipoamide.

L-aspartic acid, L-aspartate, D-aspartic acid, DL-alanine, L-alanine, D-alanine, β-alanine, L-arginine, L-isorocyanine, glycine, L-glutamine, L-glutamic acid, L-cystine, derivatives of L-cysteine, L-threoin, L-serine, L-tyrosine, L-tryptophan, L-valine, L-histidine, L-phenylalanine, L-proline, DL-methionine, L-methionine, Amino acids such as L-lysine, L-leucine, glycylglycine, glutathione, oxidized glutathione, γ-aminobutyric acid, ε aminocaproic acid, L-ornithine hydrochloride, L-citrulline and the like.
Hormones such as cortisone, testosterone, thyroxine, adrenaline, and insulin.

  Adenine, adenosine, 5'-adenylic acid, 3 ', 5'-cyclic adenylic acid, adenosine triphosphate sodium salt, 6-allyl adenosine, 6-benzyl adenine, 6-allyl adenosine, 6-benzyl adenosine, dexadenosine Monophosphate, guanine, guanosine, guanylate sodium salt, deoxyguanosine monophosphate, uracil, uridine, 5'-uridylic acid disodium salt, deoxyuridine, 5'-iododeoxyuridine, uridine-5'-diphosphate glucose Orotic acid, cytosine, cytidine, 5'-cytidylic acid, cytidine-5'-triphosphate, deoxycytidine monophosphate, cytidine-5'-diphosphate choline sodium salt, arabinosylcytosine, pipeoxanthin, inosine Sodium 5'-inosinate 6-mercaptopurine, 6-methylmercaptopurine, nicotinamide mononucleotide, nicotinamide adenine dinucleotide, nicotinamide adenine dinucleotide reduced sodium salt, nicotinamide adenine dinucleotide phosphate, nicotinamide adenine dinucleotide phosphate reduced sodium salt, Nucleic acids and lipids such as cholesterol and γ-oryzanol.

  In addition, urea, N, N'-ethylenebis (stearoamide), oleic acid amide, stearic acid amide, N, N'-methylenebis (stearoamide), methylol stearamide, potassium stearate, sodium stearate, CTU, CTU guanamine , Sebacic acid, dodecanedioic acid, dodecanedioic acid dihydrazide, pentaerythritol, malonic acid, itaconic anhydride, maleic anhydride, acetanilide, acetoacetanilide, p-aminoacetanilide, isophthalic acid, dimethyl terephthalate, 4,4'-dimethoxy Benzophenone, diphenylacetic acid, diphenylsulfone, dimethyl terephthalate, hydrogenated bisphenol A, bisphenol A, bis (4-hydroxyphenyl) sulfone, P-hydroxybenzoic acid, gallic acid steer Le, laurone, the stearone like.

  Examples of the inorganic substance include calcium chloride, sodium chloride, sodium silicate, salicy powder, disodium carbonate, soda lime, aluminum silicate, aluminum sulfate, ammonium alum, ammonium sulfate, calcium carbonate, colloidal silica and the like.

  The solid matter contained in the medium is 3.0% by weight or more, preferably 3.0 to 90.0% by weight. If the amount is less than 3.0% by weight, the image-forming property is unsatisfactory. If the amount exceeds 90.0% by weight, depending on the solid material applied, the viscosity increases and the initial image-forming property tends to be impaired.

Further, in a system in which a solid material is dispersed in a liquid composition, in order to efficiently impregnate the porous material with the solid material, the particle size of the solid material is 10 μm or less, preferably 0.01 μm to 10 μm, Preferably, the thing of 0.01 micrometer-5 micrometers is used.
It is difficult to finely disperse a solid material to 0.01 μm or less, and if it is 10 μm or more, it is difficult for solid particles to enter the voids of the porous layer, and it is difficult to form a clear image by adhering to the porous layer surface. Become.

  In addition, when water-soluble material is used as the solid material, the liquid medium evaporates from the written liquid composition, and the image formed by the solid material can be removed by washing with water, so that the image becomes unnecessary. In this case, the indicator can be used repeatedly without discarding the indicator when image formation fails. In addition, the solid matter on the hand can be easily washed away with water.

Further, when a shear thinning agent is added to the liquid composition, the liquid composition is prevented from leaking from the pen tip when the writing instrument filled with the liquid composition is not used, or the writing tip is directed upward (correctly). The backflow of the liquid composition when left in a standing state can be prevented.
Furthermore, since it is possible to prevent bleeding of characters and images formed on the porous layer, clear handwriting can be formed.
In particular, the viscosity of the liquid composition to which the shear thinning agent is added is 200 to 3000 mPa · s at a shear rate of 3.84S ⁻¹ by an E-type rotational viscometer at 20 ° C. It is preferable that the shear thinning index is 0.1 to 0.6.
The shear thinning index (n) is expressed by an empirical formula T = Kj ⁿ (K is a non-Newtonian viscosity coefficient) obtained from rheological measurement by a viscometer such as a shear stress value (T) and a shear rate value (j). It is a value calculated by fitting.
Examples of the shear thinning agent include xanthan gum, welan gum, succinoglycan (average molecular weight of about 1 to 8 million) whose constituent monosaccharide is an organic acid-modified heteropolysaccharide of glucose and galactose, alka gum, guar gum, locust bean gum and A gel having a gelling ability extracted from seaweeds such as glucomannan, agar and carrageenan, polymers having a molecular weight of 100,000 to 150,000 mainly composed of derivatives thereof, hydroxyethyl cellulose, alginic acid alkyl esters, and alkyl esters of methacrylic acid. Viscous polysaccharides, benzylidene sorbitol and benzylidene xylitol or derivatives thereof, crosslinkable acrylic acid polymer, inorganic fine particles, polyglycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyethylene glycol fatty acid ester , Polyoxyethylene alkyl ether, polyoxypropylene alkyl ether, polyoxyethylene alkylphenyl ether, fatty acid amide and other nonionic surfactants having an HLB value of 8 to 12, salts of dialkyl or dialkenylsulfosuccinic acid, N-alkyl Examples thereof include a mixture of -2-pyrrolidone and an anionic surfactant, and a mixture of polyvinyl alcohol and an acrylic resin.

When the ballpoint pen form is applied as the writing instrument, the medium includes a higher fatty acid such as oleic acid, a nonionic surfactant having a long-chain alkyl group, a polyether-modified silicone oil, a thiophosphorous acid tri (alkoxycarbonylmethyl ester). ) And thiophosphite triester (alkoxycarbonylethyl ester), etc., polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether phosphate monoester, polyoxyethylene alkyl ether or polyoxyethylene alkyl aryl ether It is preferable to add a lubricant such as a phosphoric acid diester or a metal salt, an ammonium salt, an amine salt, an alkanolamine salt thereof to give the ball seat an antiwear effect.
In addition, benzotriazole, tolyltriazole, dicyclohexylammonium nitrite, diisopropylammonium nitrite, saponin and other rust preventives, coalic acid, sodium salt of 1,2-benzthiazolin-3-one, sodium benzoate, dehydro as necessary Uses preservatives or antifungal agents such as sodium acetate, potassium sorbate, propyl paraoxybenzoate, 2,3,5,6-tetrachloro-4- (methylsulfonyl) pyridine, wetting agents, antifoaming agents, and dispersing agents May be. Further, colorants such as general dyes and pigments, fluorescent dyes and pigments can be added.
Moreover, an acrylic resin, a styrene maleic acid copolymer resin, polyvinyl pyrrolidone, polyvinyl alcohol, dextrin, etc. can also be used for adhesion and viscosity imparting.

As a writing instrument incorporating the liquid composition, a marking pen, a ballpoint pen, a brush pen, or the like can be applied, and a cap-type or a retractable type may be used.
As the marking pen, the structure and shape of the marking pen are not particularly limited. For example, a marking pen tip such as a fiber tip, a felt tip, or a plastic tip is attached to the writing tip and accommodated inside the shaft cylinder. A structure in which a liquid composition composed of fiber bundles is impregnated with a liquid composition and the liquid composition is supplied to the tip of the writing, and the liquid composition is accommodated directly inside the shaft tube, and a comb-fluid-shaped liquid flow rate adjusting member or fiber bundle A structure in which a predetermined amount of a liquid composition is supplied to a writing tip portion through a liquid flow rate adjusting member comprising: a liquid composition is accommodated directly in the shaft tube, and a predetermined amount of liquid composition is supplied to the writing tip portion by a valve mechanism A marking pen having a structure for supplying an object can be mentioned.

As the ballpoint pen, the structure and shape of the ballpoint pen itself are not particularly limited. For example, a writing tip portion in which a liquid occlusion body composed of a fiber bundle housed in a shaft tube is impregnated with a liquid composition and a ballpoint pen tip is attached. The liquid composition is supplied directly to the inside of the shaft cylinder, and the liquid composition is accommodated directly inside the shaft tube, and a predetermined amount of liquid is applied to the writing tip portion by interposing a liquid flow rate adjusting member composed of a comb groove-like liquid flow rate or a fiber bundle. A structure for supplying the composition, a liquid containing tube filled with the liquid composition in the shaft cylinder, the liquid containing tube communicating with the ball-point pen tip, and a liquid for preventing backflow on the end face of the liquid composition A ballpoint pen having a structure in which a stopper is provided can be exemplified.
The ballpoint pen tip is a ball holder formed by cutting with a tip holding a ball in a ball holding portion formed by pressing and deforming the vicinity of the tip of a metal pipe inward from the outer surface, a metal material drill or the like. Examples include a chip holding a ball in the holding portion, a chip holding a ball by providing a resin ball receiving seat inside a metal or plastic molded body, and the like. The tip may be configured to bias the ball forward by a spring body.
The ball may be about 0.1 to 3.0 mm in diameter, such as cemented carbide, stainless steel, ruby, ceramic, resin, rubber, etc., preferably 0.3 to 1.5 mm, more preferably 0. 3 to 1.0 mm are used.

When taking the form which accommodates the said liquid composition in a liquid accommodation pipe | tube, an ink backflow prevention body composition can be filled into the rear end of a liquid composition as needed.
The ink backflow preventive composition is composed of a non-volatile liquid or a hardly volatile liquid, and specifically includes petroleum jelly, spindle oil, castor oil, olive oil, refined mineral oil, liquid paraffin, polybutene, α-olefin, and α-olefin. Examples include oligomers or co-oligomers, dimethyl silicone oil, methylphenyl silicone oil, amino-modified silicone oil, polyether-modified silicone oil, fatty acid-modified silicone oil, and the like, and one or more can be used in combination.
Further, it is preferable to add a gelling agent to the non-volatile liquid and / or the hardly volatile liquid to increase the viscosity to a suitable viscosity. The surface of the silica is hydrophobically treated, the surface of the silica is methylated, Aluminum silicate, swelling mica, clay-based thickeners such as bentonite and montmorillonite with hydrophobic treatment, fatty acid metal soap such as magnesium stearate, calcium stearate, aluminum stearate, zinc stearate, tribenzylidene sorbitol, fatty acid amide, Examples thereof include amide-modified polyethylene wax, hydrogenated castor oil, dextrin compounds such as fatty acid dextrin, and cellulose compounds.
Furthermore, the liquid ink backflow prevention body composition and a solid backflow prevention body can be used in combination.

  In particular, the writing instrument is preferably a ballpoint pen equipped with a ballpoint pen tip that holds a ball rotatably. In the ball-point pen, fine characters can be written and handwriting bleeding can be easily suppressed by adding a shear thinning agent, which is optimal for writing on the indicator of the present invention.

  Examples are shown below, but the present invention is not limited to the examples. In addition, the part in an Example shows a weight part. The brightness value was measured using a color difference meter [TC3600 type color difference meter, manufactured by Tokyo Denshoku Co., Ltd.].

Example 1 (see FIG. 1)
On high-quality paper (support 2) on which the red colored layer 3 is printed, 15 parts of wet-process silicic acid [trade name: NIPSEAL E-200, manufactured by Nippon Silica Kogyo Co., Ltd.], urethane emulsion [trade name: Hydran HW- 930, manufactured by Dainippon Ink & Chemicals, Inc., solid content 50%] 30 parts, water 50 parts, silicone-based antifoaming agent 0.5 part, aqueous ink thickener 3 parts, ethylene glycol 1 part, isocyanate system Using a white screen printing ink obtained by uniformly mixing and stirring 3 parts of a crosslinking agent, solid printing was performed on a 100-mesh screen plate, followed by drying and curing to form a porous layer 4.
Next, 15 parts of palmitic acid (melting point 57 ° C.), 30 parts of acrylic emulsion [trade name: Neocyl A614, manufactured by Avicia Co., Ltd.], 0.5 part of antifoaming agent, 3 parts of thickener for water-based ink were dispersed. A wax layer 5 was formed by printing the resulting coating solution on the porous layer 4. Furthermore, the irreversible temperature indicator 1 was obtained by providing the transparent sheet made from PET so that the said wax layer 5 (top surface) may be coat | covered, and sticking it by the support 2 edge part.

When the irreversible temperature indicator 1 is in a dry state, the white color of the porous layer 4 and the wax layer 5 is visually recognized. However, in an environment of 57 ° C. or higher, the palmitic acid of the wax layer 5 is dissolved, and the lower porous layer 4 Therefore, the porous layer 4 absorbs liquid and changes from a white opaque state to a colorless and transparent state. Therefore, the color tone of the lower red colored layer 3 was visually recognized.
The irreversible temperature indicator 1 has a lightness value (Vd) before use of 8.48, a lightness value (Vw) after use (after wax dissolution) of 5.08, and a lightness difference (Vd−Vw) of 3.8. 40. For this reason, the color change before and after use is clear and suitable for use in a dark place.

Example 2 (see FIG. 2)
On high-quality paper (support 2) on which the red colored layer 3 is printed, 15 parts of stearic acid (melting point 69 ° C.), 30 parts of acrylic emulsion [trade name: Neocyl A614, manufactured by Avicia Co., Ltd.], antifoaming agent 0. A wax layer 5 was formed by printing and drying and curing a coating solution in which 5 parts and 3 parts of a thickener for water-based ink were dispersed. Next, wet process silicic acid [trade name: Nipseal E-200, manufactured by Nippon Silica Industry Co., Ltd.] 15 parts, urethane emulsion [trade name: Hydran HW-930, manufactured by Dainippon Ink & Chemicals, Inc., solid content 50 %] White screen obtained by uniformly mixing and stirring 30 parts, 50 parts of water, 0.5 part of a silicone-based antifoaming agent, 3 parts of a thickener for water-based ink, 1 part of ethylene glycol, and 3 parts of an isocyanate-based crosslinking agent. A solid layer was printed on a 100-mesh screen plate using a printing ink and dried and cured to form a porous layer 4. Furthermore, an irreversible temperature indicator 1 was obtained by providing a transparent sheet made of PET so as to cover the upper surface (uppermost surface) of the porous layer 4 and sticking it at the edge of the support 2.

In the irreversible temperature indicator 1, the white color of the porous layer 4 and the wax layer 5 is visually recognized in a dry state, but in an environment of 69 ° C. or higher, the stearic acid of the wax layer 5 is dissolved, and the upper porous layer 4 Therefore, the porous layer 4 absorbs liquid and changes from a white opaque state to a colorless and transparent state. Therefore, the color tone of the lower red colored layer 3 was visually recognized.
The irreversible temperature indicator 1 has a lightness value (Vd) before use of 8.42, a lightness value (Vw) after use (after wax dissolution) of 5.43, and a lightness difference (Vd−Vw) of 2.4. 99. For this reason, the color change before and after use is clear and suitable for use in a dark place.

Example 3 (see FIG. 3)
On the synthetic paper (support 2) on which the black colored layer 3 is printed, 15 parts of wet-process silicic acid [trade name: NIPSEAL E-200, manufactured by Nippon Silica Kogyo Co., Ltd.], urethane emulsion [trade name: Hydran HW- 930, manufactured by Dainippon Ink & Chemicals, Inc., solid content 50%] 30 parts, water 50 parts, silicone-based antifoaming agent 0.5 part, aqueous ink thickener 3 parts, ethylene glycol 1 part, isocyanate system Using a white screen printing ink obtained by uniformly mixing and stirring 3 parts of a crosslinking agent, solid printing was performed on a 100-mesh screen plate, followed by drying and curing to form a porous layer 4. Next, 15 parts of palmitic acid (melting point 57 ° C.), 30 parts of acrylic emulsion [trade name: Neocyl A614, manufactured by Avicia Co., Ltd.], 0.5 part of antifoaming agent, 3 parts of thickener for water-based ink were dispersed. A wax layer 5 was formed by printing the resulting coating solution on the porous layer 4. Next, a transparent sheet made of PET was provided so as to cover the wax layer 5 (uppermost surface), and was stuck on the edge of the support 2. Furthermore, the irreversible temperature indicator 1 which can be stuck was obtained by providing the adhesion layer 7 provided with the peeling sheet (not shown) in the back surface (surface in which the colored layer is not provided) of the support body 2. FIG.

When the irreversible temperature indicator 1 is in a dry state, the white color of the porous layer 4 and the wax layer 5 is visually recognized. However, in an environment of 57 ° C. or higher, the palmitic acid of the wax layer 5 is dissolved, and the lower porous layer 4 Therefore, the porous layer 4 absorbs liquid and changes from a white opaque state to a colorless and transparent state. Therefore, the color tone of the lower black colored layer 3 was visually recognized.
The irreversible temperature indicator 1 has a lightness value (Vd) before use of 8.20, a lightness value (Vw) after use (after wax dissolution) of 4.46, and a lightness difference (Vd−Vw) of 3. 74. Therefore, the color change before and after use is clear, and it is suitable for use in a dark place or a place that is difficult to see.

Example 4 (see FIG. 4)
Using a wax-containing support 2 in which the surface of black fine paper was impregnated with dissolved stearyl caprate (melting point: 39 ° C.), a wet process silicic acid [trade name: NIPSEAL E-200, Nippon Silica Industrial Co., Ltd.] 15 parts, urethane emulsion [trade name: Hydran HW-930, Dainippon Ink & Chemicals, solid content 50%] 30 parts, water 50 parts, silicone-based antifoaming agent 0.5 White screen printing ink obtained by uniformly mixing and agitating 3 parts of a thickener for water-based ink, 1 part of ethylene glycol and 3 parts of an isocyanate-based crosslinking agent on a 100-mesh screen plate and drying. The porous layer 4 was formed by curing. Next, a transparent sheet made of PET was provided so as to cover the upper surface (upper surface) of the porous layer 4 and adhered at the edge of the support 2. Furthermore, the irreversible temperature indicator 1 which can be stuck was obtained by providing the adhesive layer 7 provided with the peeling sheet (not shown) in the back surface of the support body 2. FIG.

In the irreversible temperature indicator 1, the white color of the porous layer 4 is visually recognized in a dry state, but in an environment of 39 ° C. or higher, the stearyl caprate which is the wax component in the support 2 is dissolved and the upper layer porous material is dissolved. Since it penetrates into the layer 4, the porous layer 4 absorbs liquid and changes from a white opaque state to a colorless and transparent state. Therefore, the color tone of the lower black support 2 was visually recognized.
The irreversible temperature indicator 1 has a lightness value (Vd) before use of 8.12, a lightness value (Vw) after use (after wax dissolution) of 4.30, and a lightness difference (Vd−Vw) of 3.30. 82. Therefore, the color change before and after use is clear, and it is suitable for use in a dark place or a place that is difficult to see.

Example 5 (see FIGS. 5 and 7)
An irreversible temperature indicator 1 was obtained in the same manner as in Example 2 except that the transparent sheet 6 made of PET was provided separately. A transparent adhesive is applied to the entire surface of the transparent sheet 6 and a release sheet is attached.

Preparation of a ballpoint pen-type writing instrument 30.0 parts of a water-soluble nylon resin, 0.3 part of succinoglycan (shear thinning agent), 0.5 part of a phosphate ester surfactant, and 69.2 parts of water are mixed, A liquid composition was prepared.
The liquid composition 95 was sucked and filled into a storage pipe 91 made of a polypropylene pipe and connected to a ballpoint pen tip 93 through a resin connection member 92. Next, a refill 9 was obtained by filling a backflow preventive composition 96 having viscoelasticity mainly composed of polybutene from the rear part of the housing tube 91.
The refill 9 was assembled to the shaft tube 10 and the cap 11 was fitted, and then a deaeration process was performed by a centrifugal process to obtain a ballpoint pen-type writing instrument 8.
The ball-point pen tip 93 has a ball holding portion formed by cutting a metal material with a drill to hold a 0.7 mm diameter hard metal ball, and the ball is moved forward by a spring body. It is energized.

When writing is performed on the porous layer 4 of the indicator 1 using the obtained ballpoint pen-type writing instrument 8, the porous layer 4 absorbs the liquid composition to be transparent, and a red handwriting is formed by the lower non-discoloring layer. It was done.
The handwriting has no blur and can be clearly entered with fine characters. After writing desired information such as date, the transparent sheet 6 (transparent adhesive portion) from which the release sheet has been peeled off is attached. This became a more practical irreversible temperature indicator.
In addition, since the solid substance contained in the liquid composition is soluble in water, even if the liquid composition adheres to the hand when forming the handwriting, it can be easily washed off with water, and the wrong handwriting can be removed. Even if it was formed, the handwriting could be completely removed by washing the indicator (porous surface) with water, and the handwriting could be formed again on the porous layer after drying.
In addition, even if an irreversible indicator with handwriting (no transparent sheet attached) is left for 3 months in an environment of 20 ° C, it maintains the same color density and shape as the initial stage, and is stable in storage. It was excellent in nature.

In the irreversible temperature indicator 1, the white color of the porous layer 4 and the wax layer 5 is visually recognized in the dry state (normal temperature range), and the information entered by the writing instrument is visually recognized in red, and this state is maintained for a long time. . Under an environment of 69 ° C. or higher, the stearic acid in the wax layer 5 dissolves and penetrates into the upper porous layer 4, so that the porous layer 4 absorbs liquid and changes from a white opaque state to a colorless and transparent state. Therefore, the color tone of the lower red colored layer 3 was visually recognized.
The irreversible temperature indicator 1 has a lightness value (Vd) before use of 8.42, a lightness value (Vw) after use (after wax dissolution) of 5.43, and a lightness difference (Vd−Vw) of 2.4. 99. For this reason, the color change before and after use is clear and suitable for use in a dark place.

Example 6 (see FIGS. 6 and 7)
An irreversible temperature indicator 1 was obtained in the same manner as in Example 4 except that the transparent sheet 6 made of PET was provided separately. The transparent sheet 6 is coated with a transparent adhesive on the edge and a release sheet is attached.

Preparation of a ballpoint pen-type writing instrument 40.0 parts of polyvinyl pyrrolidone, 0.3 part of succinoglycan (shear thinning agent), 5 parts of glycerin, 0.5 part of phosphate ester surfactant, 54.2 parts of water mixed Then, a liquid composition for a discolored body was prepared.
The liquid composition 95 was sucked and filled into a storage pipe 91 made of a polypropylene pipe and connected to a ballpoint pen tip 93 through a resin connection member 92. Next, a refill 9 was obtained by filling a backflow preventive composition 96 having viscoelasticity mainly composed of polybutene from the rear part of the housing tube 91.
The refill 9 was assembled to the shaft tube 10 and the cap 11 was fitted, and then a deaeration process was performed by a centrifugal process to obtain a ballpoint pen-type writing instrument 8.
The ball-point pen tip 93 is formed by holding a cemented carbide ball having a diameter of 0.5 mm at the tip of a tip obtained by pressing and deforming the vicinity of the tip of a metal pipe inward from the outer surface, and The ball is urged forward by a spring body.

When writing is performed on the porous layer 4 of the indicator 1 using the obtained ballpoint pen-type writing instrument 8, the porous layer 4 absorbs the liquid composition to be transparent, and the black handwriting by the lower black support 2 is formed. Been formed.
The handwriting has no blur and can be clearly entered with fine characters. After writing desired information such as date, the transparent sheet 6 (transparent adhesive portion) from which the release sheet has been peeled off is attached. This became a more practical irreversible temperature indicator.
In addition, since the solid substance contained in the liquid composition is soluble in water, even if the liquid composition adheres to the hand when forming the handwriting, it can be easily washed off with water, and the wrong handwriting can be removed. Even if it was formed, the handwriting could be completely removed by washing the indicator (porous surface) with water, and the handwriting could be formed again on the porous layer after drying.
In addition, even if an irreversible indicator with handwriting (no transparent sheet attached) is left for 3 months in an environment of 20 ° C, it maintains the same color density and shape as the initial stage, and is stable in storage. It was excellent in nature.

In the irreversible temperature indicator 1, the white color of the porous layer 4 is visually recognized in a dry state (normal temperature range), and the information entered by the writing instrument is visually recognized as black, and this state is maintained for a long time.
Under an environment of 39 ° C. or higher, stearyl caprate, which is a wax component in the support 2, dissolves and penetrates into the upper porous layer 4, so that the porous layer 4 absorbs liquid and becomes colorless and transparent from a white opaque state. Change to state. Therefore, the color tone of the lower black support 2 was visually recognized.
The irreversible temperature indicator 1 has a lightness value (Vd) before use of 8.12, a lightness value (Vw) after use (after wax dissolution) of 4.30, and a lightness difference (Vd−Vw) of 3.30. 82. Therefore, the color change before and after use is clear, and it is suitable for use in a dark place or a place that is difficult to see.

Comparative Example 1
In the irreversible temperature indicator 1 obtained in Example 1, the irreversible temperature indicator 1 was obtained with the same configuration except that the porous layer 4 was replaced with Japanese paper (weight per unit area: 45.2 g / m ² ).
When the irreversible temperature indicator 1 is in a dry state, the white color of the Japanese paper and the wax layer 5 is visually recognized. In an environment of 57 ° C. or higher, the palmitic acid of the wax layer 5 dissolves and penetrates into the lower Japanese paper. The color tone of the colored layer 3 was visually recognized.
The irreversible temperature indicator 1 has a lightness value (Vd) before use of 7.57, a lightness value (Vw) after use (after wax dissolution) of 6.45, and a lightness difference (Vd−Vw) of 1. It was 12. For this reason, the color tone of the lower layer can be visually recognized even before use, and the color tone of the lower layer cannot be clearly seen even after use, so that the color change before and after use cannot be clearly obtained.

Comparative Example 2
In the irreversible temperature indicator 1 obtained in Example 1, the irreversible temperature indicator 1 was obtained with the same configuration except that the porous layer 4 was replaced with a non-woven fabric (weight per unit area 34.7 g / m ² ).
In the irreversible temperature indicator 1, the white color of the nonwoven fabric and the wax layer 5 is visually recognized in a dry state, and the palmitic acid of the wax layer 5 dissolves and penetrates into the nonwoven fabric of the lower layer in an environment of 57 ° C. or higher. The color tone of the colored layer 3 was visually recognized.
The irreversible temperature indicator 1 has a lightness value (Vd) before use of 6.60, a lightness value (Vw) after use (after wax dissolution) of 6.35, and a lightness difference (Vd−Vw) of 0.6. 25. For this reason, the color tone of the lower layer can be visually recognized even before use, and the color tone of the lower layer cannot be clearly seen even after use, so that the color change before and after use cannot be clearly obtained.

DESCRIPTION OF SYMBOLS 1 Irreversible temperature indicator 2 Support body 3 Colored layer 4 Porous layer 5 Wax layer 6 Transparent sheet 7 Adhesive layer 8 Ball-point pen 9 Refill 91 Housing tube 92 Connection member 93 Ball-point pen tip 94 Tail plug 95 Liquid composition 96 Backflow prevention body composition 10 Shaft cylinder 11 Cap

Claims (9)

  On the colored support, a low-refractive-index pigment is fixed in a dispersed state in a binder resin, and a non-liquid-absorbing porous layer that is opaque and transparent in the liquid-absorbing state is provided. An irreversible temperature indicator with a wax layer that melts at temperature.   A wax layer that dissolves at a specific temperature is provided on a colored support, and a low refractive index pigment is fixed to a binder resin in a dispersed state on the wax layer, and is opaque in a non-liquid absorbing state and transparent in a liquid absorbing state. An irreversible temperature indicator provided with a porous layer.   On a colored support impregnated with a wax that dissolves at a specific temperature, a low-refractive-index pigment is fixed to a binder resin in a dispersed state, and is provided with a porous layer that is opaque in the non-absorbing state and transparent in the absorbing state. An irreversible temperature indicator.   The irreversible temperature indicator according to any one of claims 1 to 3, wherein a transparent sheet is provided on the uppermost surface.   The irreversible temperature indicator according to any one of claims 1 to 4, wherein a difference between a brightness value before dissolving the wax and a brightness value after dissolving the wax is 2.0 or more.   The irreversible temperature indicator according to any one of claims 2 to 5 and a writing instrument incorporating a liquid composition in which a solid material having a refractive index of 1.3 to 1.8 is dissolved and / or dispersed in a liquid medium. An irreversible temperature indicator set.   The irreversible temperature indicator set according to claim 6, wherein a particle size of the solid material dispersed in the liquid medium is 10 μm or less.   The irreversible temperature indicator set according to claim 6 or 7, wherein a shear thinning agent is contained in the liquid medium.   The irreversible temperature indicator set according to any one of claims 6 to 8, wherein the writing instrument is in the form of a ballpoint pen with a ballpoint pen tip holding a ball rotatably.

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